1-Dodecene → 2,6-Diformyl-4-(dodecen-1-yl)phenol

HRID 229717

Reaction equation

HRID 229717 reaction equation
[CH:1]([C:3]1[CH:8]=[C:7](Br)[CH:6]=[C:5]([CH:10]=[O:11])[C:4]=1[OH:12])=[O:2].[CH2:13]=[CH:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24].C([O-])(O)=O.[Na+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C([O-])(=O)C.C([O-])(=O)C.[Pd+2]>[CH:1]([C:3]1[CH:8]=[C:7]([CH:13]=[CH:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[CH:6]=[C:5]([CH:10]=[O:11])[C:4]=1[OH:12])=[O:2]

Participants

6

Reactant 3

HCID 81831-DodeceneHCID 516892Sodium BicarbonateHCID 52602065-Bromo-2-hydroxybenzene-1,3-dicarbaldehyde

Product 1

HCID 858556222,6-Diformyl-4-(dodecen-1-yl)phenolYield 51%

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
82 °C

Procedure

2,6-Diformyl-4-bromophenol (1.00 g, 4.37 mmol), 1-dodecene (4.8 mL, 21.7 mmol), 1.40 g tetrabutylammonium bromide (4.34 mmol), 0.50 g NaHCO3 (5.95 mmol), 1.00 g LiCI (23.6 mmol) and 0.100 g palladium diacetate (Pd(OAc)2) (0.45 mmol) were combined in 30 mL degassed anhydrous dimethylformamide (DMF). The mixture was sparged with argon for 10 min and then sealed in a pressure vial which was warmed to 82° C. and held for 40 h. The crude reaction mixture was partitioned between CH2CI2 and 0.1 M HCI solution. The organic layer was washed with 0.1 M HCI (2×), brine (2×), and saturated aqueous NaHCO3 (2×), dried over MgSO4 and concentrated under reduced pressure. The dark yellow oil was purified by column chromatography on silica gel (25% hexanes in Et2O) to give 0.700 g (51%) of the title compound as primarily the Z isomer.

Workup

  1. customdegassed anhydrous dimethylformamide (DMF)
  2. customThe mixture was sparged with argon for 10 min
  3. customsealed in a pressure vial which
  4. customThe crude reaction mixture
  5. customwas partitioned between CH2CI2 and 0.1 M HCI solution
  6. washThe organic layer was washed with 0.1 M HCI (2×), brine (2×), and saturated aqueous NaHCO3 (2×)
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated under reduced pressure
  9. customThe dark yellow oil was purified by column chromatography on silica gel (25% hexanes in Et2O)

Sources & evidence

ORD record
ord-df6876f6aec947b690b736cbf5e1fe23
Source dataset
uspto-grants-2009_07
Patent number
US07563890B2

Linked notes

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